CN112374522A - Barite high-purity purification process - Google Patents
Barite high-purity purification process Download PDFInfo
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- CN112374522A CN112374522A CN202011210997.5A CN202011210997A CN112374522A CN 112374522 A CN112374522 A CN 112374522A CN 202011210997 A CN202011210997 A CN 202011210997A CN 112374522 A CN112374522 A CN 112374522A
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- barite
- equal
- purification process
- purity
- sodium
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 title claims abstract description 169
- 239000010428 baryte Substances 0.000 title claims abstract description 113
- 229910052601 baryte Inorganic materials 0.000 title claims abstract description 113
- 238000000746 purification Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 57
- 239000012535 impurity Substances 0.000 claims abstract description 39
- 238000001354 calcination Methods 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 238000005188 flotation Methods 0.000 claims abstract description 18
- 230000001698 pyrogenic effect Effects 0.000 claims abstract description 8
- 239000006260 foam Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 21
- 238000005261 decarburization Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000004088 foaming agent Substances 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 239000003350 kerosene Substances 0.000 claims description 7
- 230000002000 scavenging effect Effects 0.000 claims description 7
- 239000002283 diesel fuel Substances 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- -1 isopropyl amyl Chemical group 0.000 claims description 4
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 3
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- ALMYWPYLYLEEKV-UHFFFAOYSA-M C(C)(=O)[O-].[Na+].C(CCCCCCCCCCCCCCCCC)N Chemical compound C(C)(=O)[O-].[Na+].C(CCCCCCCCCCCCCCCCC)N ALMYWPYLYLEEKV-UHFFFAOYSA-M 0.000 claims description 2
- VJXUJFAZXQOXMJ-UHFFFAOYSA-N D-1-O-Methyl-muco-inositol Natural products CC12C(OC)(C)OC(C)(C)C2CC(=O)C(C23OC2C(=O)O2)(C)C1CCC3(C)C2C=1C=COC=1 VJXUJFAZXQOXMJ-UHFFFAOYSA-N 0.000 claims description 2
- DSCFFEYYQKSRSV-KLJZZCKASA-N D-pinitol Chemical compound CO[C@@H]1[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@H]1O DSCFFEYYQKSRSV-KLJZZCKASA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000005262 decarbonization Methods 0.000 claims description 2
- 239000004519 grease Substances 0.000 claims description 2
- RNYJXPUAFDFIQJ-UHFFFAOYSA-N hydron;octadecan-1-amine;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH3+] RNYJXPUAFDFIQJ-UHFFFAOYSA-N 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims 2
- 239000002131 composite material Substances 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052742 iron Inorganic materials 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000005406 washing Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 abstract description 4
- 239000010452 phosphate Substances 0.000 abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 4
- 159000000007 calcium salts Chemical class 0.000 abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 24
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 19
- 239000002994 raw material Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 12
- 239000001569 carbon dioxide Substances 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- 239000002699 waste material Substances 0.000 description 10
- 239000003245 coal Substances 0.000 description 9
- 238000003763 carbonization Methods 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000010446 mirabilite Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000005484 gravity Effects 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 244000308427 ramon Species 0.000 description 1
- 235000005828 ramon Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/462—Sulfates of Sr or Ba
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B7/00—Combinations of wet processes or apparatus with other processes or apparatus, e.g. for dressing ores or garbage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a high-purity purification process of barite, which comprises impurity removal in advance, deep impurity removal and pyrogenic calcination, wherein for barite containing main impurities such as carbon (more than 5%), silicate, carbonate, calcium salt, iron (mainly scrap iron generated in the mechanical production process), phosphate and the like, the whiteness and the purity of the barite cannot reach the directly applied industrial standard, most of the impurities are removed by adopting flotation and acid washing, a large amount of scrap iron mixed in the crushing process of the barite material can be removed, high-purity barium sulfate can be directly obtained without roasting and impurity removal, and then a high-purity high-whiteness product with the purity of more than or equal to 95.0% and the whiteness of more than or equal to 90.0 can be obtained by calcining.
Description
Technical Field
The invention relates to a dressing-smelting combined process for efficient and environment-friendly purification of barite, in particular to an original method for combining mineral dressing and pyrogenic calcination without changing the original physical structure of barite, and belongs to the field of mineral dressing technology and pyrogenic calcination.
Background
With the increasing exhaustion of directly available barite resources, there are two main treatment methods for barite (mainly containing carbon/carbonate/silicate/calcium salt) with high impurity content:
firstly, the chemical method mainly produces precipitated barium sulfate, and the production process of precipitated barium sulfate mainly has two kinds at present: the mirabilite method and the sulfuric acid method.
The mirabilite method is that natural barite ore is added with coal and calcined to be converted into barium sulfide, and then the barium sulfide reacts with mirabilite (sodium sulfate) to generate precipitated barium sulfate and a byproduct sodium sulfide; the sulfuric acid method is to convert barium sulfide into barium carbonate by introducing carbon dioxide, and then react with pure sulfuric acid to generate precipitated barium sulfate.
It can be seen from the above production process of barium sulfate that the free barium, smell (residual sulfide ion), impurities, black spots and whiteness of the barium sulfate precipitated by sulfuric acid method are higher by several steps than those of the mirabilite method, and the cost is also higher by a lot, so that the barium sulfate is the most expensive precipitated barium sulfate on the market at present.
In addition, in the chemical method, barium sulfate is converted into barium carbonate, barite and raw material coal are respectively crushed and sieved, and then the weight ratio of the barite to the raw material coal is calculated according to the following formula of 100: 18-20 (by weight) are mixed, then the mixture is continuously added to the tail part of the rotary kiln, fuel coal which is finely crushed in the Raymond process is blown into the head of the rotary kiln through wind to burn and provide heat, a calcination reduction reaction is carried out to prepare a crude barium sulfide melt, the crude barium sulfide melt is conveyed into a barium melting tank through a hanging basket for a crown block, a qualified barium sulfide solution is prepared through leaching, and simultaneously leached waste residues are pulled and conveyed to a residue field to be accumulated. Pumping the qualified barium sulfide solution into a thick brine clarifying tank by a pump, heating and clarifying, conveying the solution into a carbonization tower, simultaneously introducing gaseous carbon dioxide which is gasified and decompressed by a carbon dioxide gas station into the carbonization tower, carrying out carbonization reaction on the gaseous carbon dioxide and the carbonized gaseous carbon dioxide to prepare barium carbonate slurry, carrying out solid-liquid separation by a full-automatic plate-and-frame filter press, drying by a drying rotary drum, conveying the barium carbonate slurry to a finished product packaging bin by wind, and packaging to obtain the finished barium carbonate product. The hydrogen sulfide gas generated in the carbonization process enters 1000M after gas-liquid separation in a dehydration tank3The gas holder is mixed and stored, and the by-product sulfur is prepared by adopting a Claus method.
By using a chemical method, whether precipitated barium sulfate or barium carbonate is produced, barium sulfate needs to be calcined into barium sulfide, and then barium sulfate is formed after the barium sulfate reacts with sodium sulfate, carbon dioxide, sulfuric acid and the like, the energy consumption is very high, and a plurality of intermediate products are formed, such as a sodium sulfate method which generates a large amount of sodium sulfide, a sulfuric acid method which generates a large amount of free barium and the like, and a barium carbonate production process which generates a large amount of by-products, such as sulfur and the like. These are pollutants causing environmental pollution, and the low added value is not worth recycling at present.
And the other is a direct calcination method, after the barite ore is mined out, most impurities are thrown out through washing and gravity screening to obtain the barite ore with the specific gravity larger than 4.2, the barite ore is pulverized and conveyed to a rotary kiln for high-temperature calcination, the calcination fuel is liquefied natural gas, high-purity barite particles can be obtained, and the high-purity barite particles are pulverized to obtain high-purity extinction barium sulfate. The direct calcination method has high requirements on raw materials (the specific gravity is more than 4.2), the raw materials need to be screened and washed, not only water resources but also a large amount of barite ore are wasted, so that the resource waste is caused, and meanwhile, because impurities in the barite cannot be removed in advance in a large amount, the purity of the barite in the obtained product can reach more than 95.0%, but the whiteness is between 70% and 85%, so that a high-whiteness qualified product cannot be produced.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a high-purity purification process for barite, which is used for the barite with high contents of carbon (more than 5%), silicate, carbonate, calcium salt, iron (mainly scrap iron generated in the mechanical production process), phosphate and the like as main impurities, because the whiteness and the purity of the barite cannot reach the directly applied industrial standard, the invention firstly adopts flotation and acid washing to remove most impurities, simultaneously can greatly remove scrap iron mixed in the crushing process of the barite material, can directly obtain high-purity barium sulfate without roasting to remove impurities, and then can obtain a high-purity high-whiteness product with the purity of more than or equal to 95.0% and the whiteness of more than or equal to 90.0 through calcination.
In order to achieve the technical purpose, the invention adopts the following technical scheme: a barite purification process comprises impurity removal in advance, deep impurity removal and pyrogenic calcination, and specifically comprises the following steps:
the method comprises the following steps: removing impurities in advance
Crushing barite raw ore to-200 meshes which are more than or equal to 90%, adding water to adjust the concentration of ore pulp to be 25-40%, adding a decarbonization reagent to perform flotation and decarburization to obtain a carbon-containing foam product and a decarburization barite bottom flow; adding an inhibitor, a collecting agent and a foaming agent into the decarburization barite underflow in sequence to float barite to obtain barite foam containing more than or equal to 95 percent of barite and impurity underflow containing less than or equal to 5 percent of barite;
step two: deep impurity removal
Slurry mixing the barite foam containing more than or equal to 90% of barite in the first step until the concentration is not higher than 20%, adding acid to adjust the pH value of the barite foam slurry to be 5-6, and performing filter pressing until the water content of a barite filter cake is 15-17%;
step three: pyrogenic process calcination
And (4) granulating and drying the barite filter cake obtained in the step two, and calcining at 800-1100 ℃ to obtain the barite product with the purity of more than or equal to 95.0% and the whiteness of more than or equal to 90.0.
Preferably, in the first step, the carbon removing agent is at least one selected from kerosene, oxidized kerosene, compound kerosene, No. 0 light diesel oil, No. 10 light diesel oil, MIBC (isopropyl amyl alcohol), pinitol oil, No. 2 oil, sec-octanol and mixed alcohol, and the dosage of the carbon removing agent is 10-25 g/t.
Preferably, in the first step, the flotation decarburization comprises one roughing, or one roughing and at least one scavenging. According to the method, whether scavenging is increased or not can be determined according to the carbon content in the barite raw ore and the carbon removal rate of primary roughing, and the carbon content in the barite slurry subjected to flotation decarburization is only required to be less than or equal to 0.5%.
Preferably, in the first step, the inhibitor is at least one selected from water glass, sodium lignosulfonate, water glass, sodium hexametaphosphate, trisodium phosphate and aluminum sulfate, and the dosage of the inhibitor is 200-400 g/t.
Preferably, in the first step, the collecting agent is at least one of oleic acid, sodium oleate, sodium stearate, mixed grease, sodium octadecylamine acetate and octadecylamine hydrochloride, and the dosage of the collecting agent is 200-500 g/t.
Preferably, in the first step, the foaming agent is at least one selected from sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate and the like, and the dosage of the foaming agent is 10-50 g/t.
Preferably, in the first step, the process for flotation of barite comprises one roughing, at least one scavenging and at least one concentrating.
Preferably, in the second step, the acid is hydrochloric acid or waste acid containing hydrochloric acid, the acid is added into the barite foam slurry, stirred for 5-30min and adjusted to the pH value of the barite foam slurry to 2; continuously adding acid, stirring for 5-30min, and adjusting the pH value of the barite foam slurry to 3-4; and (4) continuing to stir for 5-20min without adding acid until the final pH value of the barite foam slurry is 5-6. The invention preferably adopts a mode of adjusting the pH value in sections, is beneficial to fully mixing and reacting the barite slurry and the acid, not only prevents waste caused by excessive acid consumption, but also is beneficial to not bringing excessive chloride ions in subsequent water treatment, can fully dissolve different impurities (mainly iron, aluminum, calcium, magnesium and the like) in the barite slurry under different pH values, and is convenient for realizing high-purity extraction of the barite in the subsequent step.
Preferably, in the third step, 0.5-2kg/t of industrial salt is added in the roasting process for producing the barite product with high whiteness.
The pre-impurity removal method mainly comprises the steps of sequentially removing carbon-containing impurities through a flotation mode, then removing non-carbon impurities such as silicate and carbonate, and the like, wherein more than or equal to 98% of carbon, more than or equal to 95% of silicate, more than or equal to 80% of carbonate, more than or equal to 80% of iron and more than or equal to 80% of phosphate can be removed through flotation, and barite foam containing more than or equal to 95% of barite is obtained; then, deeply removing impurities, and mainly removing carbonate and residual partial iron in the barite foam product in an acid washing mode; and finally, carrying out pyrogenic calcination, wherein the purpose is to remove acid radical ions introduced in the acid washing deep impurity removal process and other impurities which are not removed completely in the deep impurity removal process, such as residual scrap iron and residual medicament (added in the flotation process, mainly residual silicate, organic matters and the like), and residual carbon which is not removed completely in the flotation process, and the like, so as to finally obtain the high-purity high-whiteness barite product with the purity of more than or equal to 95.0 percent and the whiteness of more than or equal to 90.0.
Compared with the prior art, the invention has the advantages that:
(1) the method firstly adopts flotation to remove most impurities, and simultaneously removes a large amount of scrap iron mixed in the process of crushing barite materials, high-purity barium sulfate can be directly obtained without roasting and impurity removal, and then a high-purity high-whiteness product with the purity of more than or equal to 95.0 percent and the whiteness of more than or equal to 90.0 can be obtained by calcining.
(2) Compared with the direct calcining method which requires that the proportion of the barite raw ore is more than or equal to 4.2, the method has no requirement on the proportion content of the barite raw ore, has low requirement on raw materials and wide application range; compared with the chemical method (sulfuric acid method) which produces barium sulfate, the consumption of sulfuric acid is large (300-500kg/t), and the reaction is carried out at 80 ℃, only a small amount of acid solution (20-70kg/t, corresponding to the dry weight of barium sulfate) needs to be added in the acid washing process, and the acid washing process is normal temperature and normal pressure, and the process is simple.
(3) The barite mineral of the invention is continuously removed of impurities from mining to finished products, does not produce intermediate products (barium sulfide), does not participate in any chemical reaction, and does not change the original crystal lattice form of the barite mineral.
(4) The water used in the impurity removal in advance and the deep impurity removal stage belongs to closed cycle, and is not required to be discharged outside, so that the environment is not influenced.
(5) The flotation process and the deep impurity removal (acid washing) process are carried out at normal temperature and normal pressure, the process requirement is simple, the actual operation is simple, the equipment is simple, and the equipment investment is less.
Detailed Description
The present invention is further described with reference to the following examples, but the scope of the present invention is not limited to the examples.
Example 1
In the barite (mass percent), carbon content is more than or equal to 1.0 percent, silicate is more than or equal to 5.0 percent, carbonate is more than or equal to 5.0 percent, phosphate is more than or equal to 0.5 percent, barium sulfate is more than or equal to 70 percent, and other impurities, such as iron and iron compounds, manganese oxides, other aluminum-magnesium-sodium salt-containing complex compounds and the like.
(1) Crushing the barite raw ore to the particle size of-200 meshes (0.074mm) or more than 90%, and then feeding the crushed barite raw ore into a stirring barrel for size mixing until the concentration of ore pulp is 25-40%;
(2) adding 10-25g/t of kerosene, 5-10g/t of diesel oil and 10-15g/t of MIBC (isopropyl amyl alcohol) into the ore pulp, stirring for 3-7min, sending to a flotation column, and performing primary roughing and primary scavenging decarburization, wherein the top overflow material is a carbon-containing foam product, and the bottom outflow material is a decarburization barite bottom flow;
(3) adding an inhibitor (water glass 200-400g/t, aluminum sulfate 50-80g/t), a collector (sodium oleate 100-150g/t, sodium stearate 10-100g/t) and a foaming agent (sodium dodecyl benzene sulfonate 20-30g/t) into the decarburization barite underflow, stirring for 3-15min, sending to a flotation column, and performing primary roughing, primary scavenging and primary fine flotation on barite, wherein the overflow material at the top is a barite foam product, the outflow material at the bottom is an impurity removal tail flow, and the outflow material at the bottom can be treated as waste after pressure filtration, and can also be used as a raw material such as baking-free bricks;
(4) mixing the barite foam product to a concentration not higher than 20%, adding hydrochloric acid or waste acid containing hydrochloric acid, stirring for 5-30min, and adjusting to a pH value of the barite foam slurry of about 2; continuously adding hydrochloric acid or waste acid containing hydrochloric acid, stirring for 5-30min, and adjusting the pH value of the barite foam slurry to be about 3-4; continuously stirring for 5-20min until the final pH value of the barite foam slurry is 5-6; then carrying out filter pressing by a filter press until the water content of the barite filter cake is 15-17%;
(5) and (3) granulating and drying the barite filter cake, then sending the barite filter cake to a rotary kiln, and calcining the barite filter cake for 60-120min at 800-1100 ℃ to obtain the barite product with the purity of more than or equal to 95.0% and the whiteness of more than or equal to 90.0.
Comparative example 1: direct calcination process
The direct calcining process flow comprises the following steps: raw materials- -washing and screening- -lump ore (specific gravity 4.20) - -, powdering- -calcining- -powdering- -packaging- -to obtain the finished product.
The direct calcination method comprises the following steps:
(1) crushing the barite raw ore by a jaw crusher, washing with water and screening to obtain a barite raw material with the specific gravity of 4.20;
(2) grinding barite raw material with specific gravity of 4.20 (dry grinding by Raymond mill) to-200 meshes of more than or equal to 90%;
(3) and conveying the powdered barite powder to a rotary kiln, and calcining at 800-1100 ℃ for 180min for 100-180min to obtain the barite product with the purity of 90-95% and the whiteness of not higher than 82%.
The direct calcination method has higher requirements on raw materials, thereby causing resource waste; the requirement on the impurity content of the raw material is high, and the obtained barite product has poor quality.
Comparative example 2: chemical method for producing precipitated barium sulfate
(1) Powdering the screened barite raw material (dry powdering by a Raymond mill);
(2) mixing barite raw material powder with coal according to a certain proportion;
(3) continuously adding the mixed barite powder and coal mixture into a rotary kiln for calcining, and converting barite (barium sulfate) into barium sulfide;
(4) mirabilite method: reacting the calcined barium sulfide with mirabilite (sodium sulfate) to generate precipitated barium sulfate and a byproduct sodium sulfide;
a sulfuric acid method: and introducing carbon dioxide into the calcined barium sulfide for size mixing to convert the barium sulfide into barium carbonate, and then reacting the barium carbonate with pure sulfuric acid to generate precipitated barium sulfate.
Both of the above two chemical methods require that barium sulfate is calcined into barium sulfide, and then the barium sulfate is formed after the barium sulfate reacts with sodium sulfate, carbon dioxide, sulfuric acid and the like, the required energy consumption is very high, and a plurality of intermediate products are formed, for example, a sodium sulfide is generated in a mirabilite method, a free barium is generated in a sulfuric acid method, and the like, a large amount of by-products such as sulfur is generated in a barium carbonate production process, and the by-products are pollutants causing environmental pollution, and the added value is low, so that the recycling is not worth at present.
Comparative example 3: chemical method for producing barium carbonate
(1) After the barite and the raw material coal are respectively crushed and screened, the barite and the raw material coal are mixed by a microcomputer according to the weight ratio of 100: 18-20 (by weight) mixing;
(2) then continuously adding the mixture to the tail of the rotary kiln;
(3) the fuel coal after the ramon procedure is finely crushed is blown into a rotary furnace end by wind to be burnt to provide heat, and the calcination reduction reaction is carried out to prepare a crude barium sulfide melt;
(4) conveying the barium sulfide to a barium sulfide tank through a hanging basket for a crown block, and leaching to obtain a qualified barium sulfide solution;
(5) pumping the qualified barium sulfide solution into a thick brine clarifying tank by a pump, heating and clarifying, conveying the solution into a carbonization tower, introducing gaseous carbon dioxide gasified and decompressed by a carbon dioxide gas station into the carbonization tower, and performing carbonization reaction on the gaseous carbon dioxide and the carbonized gaseous carbon dioxide to obtain barium carbonate slurry;
(6) and after solid-liquid separation by a full-automatic plate-and-frame filter press, drying by a drying rotary drum, and conveying to a finished product packaging bin by wind for packaging to obtain a finished barium carbonate product.
(7) The hydrogen sulfide gas generated in the carbonization process enters 1000M after gas-liquid separation in a dehydration tank3The gas holder is mixed and stored, and the by-product sulfur is prepared by adopting a Claus method.
A large amount of toxic hydrogen sulfide gas is generated in the barium carbonate production process, strict requirements are imposed on safety production and equipment, serious potential safety hazards exist, and the production cost is high. Meanwhile, a large amount of leached waste residues are generated, and secondary pollution is easily caused when the waste residues cannot be properly treated.
Claims (9)
1. The barite purification process is characterized by comprising impurity removal in advance, deep impurity removal and pyrogenic calcination, and specifically comprises the following steps:
the method comprises the following steps: removing impurities in advance
Crushing barite raw ore to-200 meshes which are more than or equal to 90%, adding water to adjust the concentration of ore pulp to be 25-40%, adding a decarbonization reagent to perform flotation and decarburization to obtain a carbon-containing foam product and a decarburization barite bottom flow; adding an inhibitor, a collecting agent and a foaming agent into the decarburization barite underflow in sequence to float barite to obtain barite foam containing more than or equal to 95 percent of barite and impurity underflow containing less than or equal to 5 percent of barite;
step two: deep impurity removal
Slurry mixing the barite foam containing more than or equal to 90% of barite in the first step until the concentration is not higher than 20%, adding acid to adjust the pH value of the barite foam slurry to be 5-6, and performing filter pressing until the water content of a barite filter cake is 15-17%;
step three: pyrogenic process calcination
And (4) granulating and drying the barite filter cake obtained in the step two, and calcining at 800-1100 ℃ to obtain the barite product with the purity of more than or equal to 95.0% and the whiteness of more than or equal to 90.0.
2. The barite purification process of claim 1, wherein: in the first step, the carbon removing agent is at least one selected from kerosene, oxidized kerosene, composite kerosene, No. 0 light diesel oil, No. 10 light diesel oil, MIBC (isopropyl amyl alcohol), pinitol oil, No. 2 oil, secondary octanol and mixed alcohol, and the dosage of the carbon removing agent is 10-25 g/t.
3. The barite purification process of claim 1, wherein: in the first step, the flotation decarburization comprises primary roughing, or primary roughing and at least one scavenging.
4. The barite purification process of claim 1, wherein: in the first step, the inhibitor is at least one selected from water glass, sodium lignosulfonate, water glass, sodium hexametaphosphate, trisodium phosphate and aluminum sulfate, and the dosage of the inhibitor is 200-400 g/t.
5. The barite purification process of claim 1, wherein: in the first step, the collecting agent is at least one of oleic acid, sodium oleate, sodium stearate, mixed grease, sodium octadecylamine acetate and octadecylamine hydrochloride, and the using amount of the collecting agent is 200-500 g/t.
6. The barite purification process of claim 1, wherein: in the first step, the foaming agent is at least one selected from sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate and the like, and the dosage of the foaming agent is 10-50 g/t.
7. The barite purification process of claim 1, wherein: in the first step, the process of flotation of the barite comprises one-time roughing, at least one-time scavenging and at least one-time concentration.
8. The barite purification process of claim 1, wherein: adding the acid into the barite foam slurry, stirring for 5-30min, and adjusting the pH value of the barite foam slurry to 2; continuously adding acid, stirring for 5-30min, and adjusting the pH value of the barite foam slurry to 3-4; and (4) continuing to stir for 5-20min without adding acid until the final pH value of the barite foam slurry is 5-6.
9. The barite purification process of claim 1, wherein: in the third step, 0.5-2kg/t of industrial salt is added in the roasting process and is used for producing the barite product with high whiteness.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4363724A (en) * | 1980-08-26 | 1982-12-14 | Alcolac, Inc. | Use of C8-34 alpha olefin sulfonates to improve and enhance the flotation and collection process used for barite |
| CN101585016A (en) * | 2009-06-22 | 2009-11-25 | 广西大学 | Low grade fluorite and barite flotation separation method |
| CN102303890A (en) * | 2011-08-19 | 2012-01-04 | 卢长生 | Production process for converting gray black barite into white barite finished product |
| CN103639059A (en) * | 2013-12-11 | 2014-03-19 | 广西大学 | Beneficiation method for carbonic mud barite ore |
| CN106269208A (en) * | 2016-08-23 | 2017-01-04 | 武汉理工大学 | A kind of baric carbonate mine reclaims the ore-dressing technique of brium carbonate |
| CN108394924A (en) * | 2018-02-10 | 2018-08-14 | 广西华洋矿源材料有限公司 | A kind of preparation method of high whiteness barite |
| CN109465114A (en) * | 2019-01-09 | 2019-03-15 | 湖南有色金属研究院 | A kind of flotation separation method of barite and dolomite |
-
2020
- 2020-11-03 CN CN202011210997.5A patent/CN112374522A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4363724A (en) * | 1980-08-26 | 1982-12-14 | Alcolac, Inc. | Use of C8-34 alpha olefin sulfonates to improve and enhance the flotation and collection process used for barite |
| CN101585016A (en) * | 2009-06-22 | 2009-11-25 | 广西大学 | Low grade fluorite and barite flotation separation method |
| CN102303890A (en) * | 2011-08-19 | 2012-01-04 | 卢长生 | Production process for converting gray black barite into white barite finished product |
| CN103639059A (en) * | 2013-12-11 | 2014-03-19 | 广西大学 | Beneficiation method for carbonic mud barite ore |
| CN106269208A (en) * | 2016-08-23 | 2017-01-04 | 武汉理工大学 | A kind of baric carbonate mine reclaims the ore-dressing technique of brium carbonate |
| CN108394924A (en) * | 2018-02-10 | 2018-08-14 | 广西华洋矿源材料有限公司 | A kind of preparation method of high whiteness barite |
| CN109465114A (en) * | 2019-01-09 | 2019-03-15 | 湖南有色金属研究院 | A kind of flotation separation method of barite and dolomite |
Non-Patent Citations (1)
| Title |
|---|
| 石贵明等: "重庆某萤石-重晶石矿浮选试验", 《现代矿业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114314631A (en) * | 2022-01-21 | 2022-04-12 | 贵州理工学院 | Treatment method for purifying and whitening barite |
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